EP1831234B1 - Compositions containing c4-swallow tail silanes - Google Patents

Compositions containing c4-swallow tail silanes Download PDF

Info

Publication number
EP1831234B1
EP1831234B1 EP05854110A EP05854110A EP1831234B1 EP 1831234 B1 EP1831234 B1 EP 1831234B1 EP 05854110 A EP05854110 A EP 05854110A EP 05854110 A EP05854110 A EP 05854110A EP 1831234 B1 EP1831234 B1 EP 1831234B1
Authority
EP
European Patent Office
Prior art keywords
group
composition according
carbon atoms
substituted
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP05854110A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1831234A1 (en
Inventor
Rudolf J. Dams
Michael S. Terrazas
George G.I. Moore
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of EP1831234A1 publication Critical patent/EP1831234A1/en
Application granted granted Critical
Publication of EP1831234B1 publication Critical patent/EP1831234B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • the present invention relates to novel fluorochemical silanes containing two perfluoro-lower alkyl groups or "tails" in close proximity to one another, called “swallow tail” silanes.
  • the novel silanes are useful as easy to clean treatments for siliceous substrates, for example, ceramics, ceramic tiles, glass, glass surfaces, and the like.
  • the novel silanes are more effective in creating high oil and water repellent surfaces compared to single group or single tail silanes of the same lower molecular tail size.
  • Fluorochemical compounds are well known and commercially used to coat or render various substrates oil- and water-repellent and to provide other desirable properties thereto such as soil repellency and soil release.
  • Fluorochemical sulfonamido silanes having at least 4 carbon atoms in the fluoroalkyl group have been described for treating substrates in GB 2,218,097 ; US 5,274,159 ; US 5,702,509 ; and earlier in US 3,492394 ; US 3,423,234 , and US 3,442,664 .
  • fluorochemical oligomeric silanes having at least 4 carbon atoms in the fluoroalkyl group have been described for treating hard surfaces, such as glass or ceramics in EP 1,369,453 ; EP 1,225,187 , and EP 1,225,188 .
  • a coating composition capable of providing a highly durable water, oil and/or stain repellent coating on a substrate.
  • a durable coating wherein the initial repellent properties are substantially maintained, even under abrading conditions.
  • the coating compositions preferably can be applied and used in an environmentally friendly way and can be produced in a reliable, convenient and cost effective way.
  • the coatings desirably have a good durability against exposure to UV light, i.e. the repellency properties do not substantially degrade upon exposure to UV light.
  • the present invention provides a fluorochemical composition containing one or more silanes of the formula I: R f SO 2 -N(R)(C n H 2n )CHZ(C m H 2m )N(R')SO 2 R f (I) wherein R f is each independently C p F 2p+1 , where p is 2 to 5; R is a C 1 to C 4 alkyl or an aryl group which is an aromatic group which is unsubstituted or substituted by one or up to five substituents selected from alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halo, hydroxy, amino, or nitro; m and n are both integers from 1 to 6; Z is a group of the formula: (C m ⁇ H 2m ⁇ )X-Q-Si(Y) 3 , in which m' is 0 to 4, X is O, S or NH and Q is -C(O)NH
  • the present invention includes a fluorochemical composition as above described with an organic solvent in an amount sufficient to dissolve and/or disperse the silane(s).
  • a third aspect of the present invention provides the above described fluorochemical composition and one or more compounds of the formula II: M(R") q (Y) r-q (II) wherein M is selected from Si, Ti, Zr, Al, V, Sn, and Zn; R" is a non-hydrolyzable group which may be the same or containing one or more silanes of formula I and, optionally one or more compounds of formula II in an organic solvent.
  • compositions of the present invention are efficient and effective oil and water repellents for siliceous surfaces, such as sanitary ceramics, ceramic tiles and glass. They provide superior overall performance to that of the single tail perfluoro C4 silanes and comparable performance to perfluoro C8 silanes.
  • the compositions are substantially free of fluorochemical compounds that eliminate slowly from living organisms and are therefore considered environmentally sustainable vis a vis materials which are based on building blocks containing a longer perfluorinated group (tail).
  • fluorochemical materials contain perfluorooctyl moieties. These surfactants ultimately degrade to perfluorooctyl-containing compounds. It has been reported that certain perfluorooctyl-containing compounds may tend to bio-accumulate in living organisms; this tendency has been cited as a potential concern regarding some fluorochemical compounds. For example, see U.S. Patent No. 5,688,884 (Baker et al. ). As a result, there is a desire for fluorine-containing compositions which are effective in providing desired surfactant properties, and which eliminate more effectively from the body (including the tendency of the composition and its degradation products).
  • fluorochemical materials of the present invention which contain perfluorobutyl moieties
  • fluorochemical materials of the present invention when exposed to biological, thermal, oxidative, hydrolytic, and photolytic conditions found in the environment, will break down to various degradation products.
  • compositions comprising perfluorobutylsulfonamido moieties are expected to degrade, at least to some extent, ultimately to perfluorobutylsulfonate salts. It has been surprisingly found that perfluorobutylsulfonate, tested in the form of its potassium salt, eliminates from the body much more effectively than perfluorohexylsulfonate and even more effectively than perfluorooctylsulfonate.
  • the fluorochemical composition contains one or more silanes of the formula I R f SO 2 -N(R)(C n H 2n )CHZ(C m H 2m )N(R')SO 2 R f (I) wherein R f is each independently C p F 2p+1 , where p is 2 to 5; R is a C 1 to C 4 alkyl or an aryl group ; m and n are both integers from 1 to 6; Z is a group of the formula: (C m H 2m )X-Q-Si(Y) 3 , in which m' is 0 to 4, X is O, S or NH and Q is -C(O)NH-(CH 2 ) n' - or -(CH 2 ) n' ; and R' is R; or Z is H, and R' is a group of the formula -(CH 2 ) n' -Si(Y) 3 ; n' is an integer of 1 to 20,
  • the perfluoroalkylsulfonamido groups may be the same or different.
  • the perfluoroalkyl may each contain 2-5 carbon atoms, but preferably each has 4 carbon atoms.
  • alkyl is defined as having 1-4 carbon atoms and includes, for example, methyl or ethyl.
  • aryl means an aromatic group such as phenyl which is unsubstituted or may be substituted by one or up to five substituents selected from alkyl, as above defined, alkoxy of 1 to 4 carbon atoms, halo (e.g. fluoro, chloro, bromo, iodo), hydroxy, amino, and nitro. Halo and alkyl substituents are preferred.
  • one embodiment has R defined as independently -CH 3 or -CH 2 CH 3 .
  • n' may also vary from 1-10 and in one embodiment may be 3.
  • a hydrolyzable group, Y, in the silanes of formula I is the same as defined for Y in the compounds of formula II below.
  • Representative fluorochemical compounds of the invention include, but are not limited to, [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOCONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , and C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 CH 2 N(SO 2 C 4 F 9 )CH 2 CH 2 CH 2 Si(OCH 3 ) 3 .
  • the fluorochemical compounds of the invention may be prepared by known methods. For example, [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOH may be made by reacting two moles of C 4 F 9 SO 2 NH(CH 3 ) with either 1,3-dichloro-2-propanol or epichlorohydrin in the presence of a base.
  • [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOCH 2 CH 2 CH 2 Si(OCH 3 ) 3 can be made from [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOH by alkylation with ClCH 2 CH 2 CH 2 Si(OCH 3 ) 3 or by alkylation with allyl chloride, followed by hydrosilation with HSiCl 3 and methanolysis. Reaction of [C 4 F 9 SO 2 N(CH 3 ) 3 CH 2 ] 2 CHOH with OCNCH 2 CH 2 CH 2 Si(OCH 3 ) 3 yields [C 4 F 9 SO 2 N(CH 3 ) 3 CH 2 ] 2 CHOCONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 .
  • composition of the present invention may include one or more organic solvents.
  • the organic solvent or blend of organic solvents used must be capable of dissolving one or more silanes of formula I and, optionally a mixture of the silanes with one or more compounds of formula II, described below.
  • Suitable organic solvents or mixtures of solvents include aliphatic alcohols, such as methanol, ethanol, isopropanol; ketones such as acetone or methyl ethyl ketone; esters such as ethyl acetate, methylformate, and ethers such as diethyl ether or dipropyleneglycol monomethylether (DPM).
  • aliphatic alcohols such as methanol, ethanol, isopropanol
  • ketones such as acetone or methyl ethyl ketone
  • esters such as ethyl acetate, methylformate
  • ethers such as diethyl ether or dipropyleneglycol monomethylether (DPM).
  • one or more silanes of formula I may be combined with one or more compounds of formula II M(R") q (Y) r-q (II) wherein M is selected from Si, Ti, Zr, Al, V, Sn, and Zn; R" is a non-hydrolyzable group different and is selected from a hydrocarbon group having from 1 to 4 carbon atoms or an aryl group which is an aromatic group which is unsubstituted or substituted by one or up to five substituents selected from alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halo, hydroxy, amino, or nitro; Y is a hydrolyzable group which may be the same or different and is selected from halogen, an alkoxy group -OR' (wherein R' represents a lower alkyl group containing 1 to 6 carbon atoms which may optionally be substituted by one or more halogen atoms), an acyloxy group
  • a fourth aspect of the present invention provides the combination of one or more silanes of formula I and one or more compounds of formula II with an organic solvent in an amount sufficient to dissolve and/or disperse both components.
  • the present invention also includes methods of treating siliceous substrates by applying to at least a portion of the surface of the substrate a fluorochemical composition ;
  • Y is a hydrolyzable group
  • Y is a hydrolyzable group which may be the same or different and is selected from halogen, an alkoxy group -OR' (wherein R' represents a lower alkyl group containing 1 to 6 carbon atoms which may optionally be substituted by one or more halogen atoms), an acyloxy group -O(CO)-R" (wherein R" represents a lower alkyl group containing 1 to 6 carbon atoms which may optionally be substituted by one or more halogen atoms), an aryloxy group -OR'" (wherein R"' represents an aryl moiety containing 6 to 12 carbon atoms, which may be
  • a fourth aspect of the present invention provides the combination of one or more silanes of formula I and one or more compounds of formula II with an organic solvent in an amount sufficient to dissolve and/or disperse both components.
  • the present invention also includes methods of treating siliceous substrates by applying to at least a portion of the surface of the substrate a fluorochemical composition; q is 0, 1 or 2, and r is 4, 3 or 2.
  • the combination may be a mixture or a condensation product obtainable after a substantially complete condensation reaction of said one or more fluorochemical silanes and said one or more non-fluorinated compounds of formula II.
  • substantially complete condensation reaction is meant that the reaction is either complete or at least 80% of the hydrolyzable groups in the mixture have disappeared, preferably at least 90%. Completion of the reaction can be monitored through the use of infrared spectroscopy and 13 C-NMR.
  • the present invention provides a composition comprising a condensation product obtainable after a partial condensation reaction of said one or more fluorochemical oligomers and said one or more non-fluorinated compounds.
  • a condensation product obtainable after a partial condensation reaction of said one or more fluorochemical oligomers and said one or more non-fluorinated compounds.
  • partial condensation and “partial condensate” in connection with the present invention is meant that some of the hydrolyzable groups in the mixture have reacted while leaving a substantial amount of hydrolyzable groups available for a condensation reaction.
  • a partial condensate means that at least 20%, preferably at least 30%, more preferably at least 50% of the hydrolyzable groups are still available for further condensation reactions.
  • hydrolyzable group in connection with the present invention refers to a group which is either directly capable of undergoing condensation reactions under appropriate conditions or which is capable of hydrolyzing under appropriate conditions, thereby yielding a compound, which is capable of undergoing condensation reactions.
  • Appropriate conditions include acidic or basic aqueous conditions, optionally in the presence of another condensation catalyst, such as Sn-compounds.
  • the hydrolyzable groups Y may be the same or different and are generally capable of hydrolyzing under appropriate conditions, for example under acidic or basic aqueous conditions, such that the fluorochemical oligomer can participate in condensation reactions.
  • the hydrolyzable groups upon hydrolysis yield groups capable of undergoing condensation reactions, such as silanol groups.
  • Hydrolyzable groups are halogens such as chlorine, bromine, iodine or fluorine, alkoxy groups -OR' (wherein R' represents a lower alkyl group containing 1 to 6, preferably 1 to 4 carbon atoms and which may optionally be substituted by one or more halogen atoms), acyloxy groups -O(CO)-R" (wherein R" represents a lower alkyl group containing 1 to 6, preferably 1 to 4 carbon atoms and which may optionally be substituted by one or more halogen atoms), aryloxy groups -OR'" (wherein R"' represents an aryl moiety containing 6 to 12, preferably containing 6 to 10 carbon atoms, which may be optionally substituted by one or more substituents independently selected from halogens, and C 1 to C 4 alkyl groups which may optionally be substituted by one or more halogen atoms).
  • R', R", and R'" may include linear, branched and/or
  • the non-hydrolyzable groups R" may be the same or different and are generally not capable of hydrolyzing under conditions for condensation reactions, e.g., acidic or basic aqueous conditions where hydrolyzable groups are hydrolyzed.
  • the non-hydrolyzable groups R" are independently a hydrocarbon group, for example an alkyl group, having from 1-4 carbon atoms as defined above for R or an aryl group also as defined above for R.
  • Representative examples of compounds of formula (II) include tetramethoxysilane, tetraethoxysilane (TEOS), methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DDS), tetraethylhexyltitanate and the like.
  • the combination or condensation product of silanes of formula I and compounds of formula II may also contain organic solvents as defined above in an amount sufficient to dissolve the compounds.
  • the weight ratio of compounds (I) to (II) is from about 100:0 to 1:99; a preferred ratio is between 50:50 and 10:90.
  • the reaction product is obtainable by reacting the components and an optional crosslinking agent.
  • the reaction product is a partial condensate or alternatively a substantially complete condensation product is formed.
  • the polycondensation reaction is conveniently carried out by mixing the starting components in an organic solvent, preferably at room temperature, in the presence of sufficient water to effect hydrolysis of the hydrolyzable groups.
  • the amount of water will be between 0.1 and 20 % by weight of the total composition, more preferably between 1 and 10% by weight.
  • an organic or inorganic acid or base catalyst should preferably be used.
  • Organic acid catalysts include acetic acid, citric acid, formic acid, triflic acid, perfluorobutyric acid and the like.
  • inorganic acids include sulphuric acid, hydrochloric acid and the like.
  • useful base catalysts include sodium hydroxide, potassium hydroxide, sodium fluoride, potassium fluoride and triethylamine.
  • the acid or base catalyst will generally be used in amounts between about 0.01 and 10%, more preferably between 0.05 and 5% by weight of the total composition.
  • composition of the present invention comprising the compounds of formulae I and II and optional crosslinking agent, and/or the partial or complete polycondensation products thereof, is generally applied to the substrate in amounts sufficient to produce a coating that is water- and oil-repellent.
  • This coating can be extremely thin, e.g., 1 to 50 molecular layers, though in practice a useful coating may be thicker.
  • Suitable substrates that can be treated in a particularly effective way with the fluorochemical composition, comprising the fluorochemical condensate mixture, of this invention include substrates having a hard surface that preferably has groups capable of reacting with the fluorinated condensate. Particularly preferred substrates include ceramics and glass.
  • Various articles can be effectively treated with the fluorochemical composition of the present invention to provide a water- and oil-repellent coating thereon. Examples include ceramic tiles, bathtubs or toilets, glass shower panels, construction glass, various parts of a vehicle (such as the mirror or windscreen), glass, and ceramic or enamel pottery materials.
  • Treatment of the substrates results in rendering the treated surfaces less retentive of soil and more readily cleanable due to the oil- and water-repellent nature of the treated surfaces. These desirable properties are maintained despite extended exposure or use and repeated cleanings because of the high degree of durability of the treated surface as can be obtained through the compositions of this invention.
  • the fluorochemical composition preferably in the form of a solvent composition as disclosed above, is applied to the substrate.
  • the amount of fluorochemical composition to be coated on the substrate will generally be that amount sufficient to produce a coating which is water- and oil-repellent, such a coating having at 20°C a contact angle with distilled water of at least 80°, and a contact angle with n-hexadecane of at least 40°, measured after drying and curing of the coating.
  • the substrate should be clean prior to applying the compositions of the invention so as to obtain optimum characteristics, particularly durability. That is, the surface of the substrate to be coated should be substantially free of organic contamination prior to coating. Cleaning techniques depend on the type of substrate and include, for example, a solvent washing step with an organic solvent, such as acetone or ethanol.
  • compositions for application to a substrate are prepared by diluting a concentrate comprising a solution of at least 25% by weight of solids in an organic solvent, by adding to the concentrate an organic solvent or mixture of solvents.
  • a wide variety of coating methods can be used to apply a composition of the present invention, such as brushing, spraying, dipping, rolling, spreading, and the like.
  • a preferred coating method for application of the fluorochemical composition includes spray application.
  • a substrate to be coated can typically be contacted with the treating composition at room temperature (typically, about 20°C to about 25°C).
  • the mixture can be applied to substrates that are preheated at a temperature of, for example, between 60°C and 150°C. This is of particular interest for industrial production, where e.g. ceramic tiles can be treated immediately after the baking oven at the end of the production line.
  • the treated substrate can be dried and cured at ambient or elevated temperature, e.g., at 40°C to 300°C and for a time sufficient to dry and cure.
  • the coating composition may be cured by irradiation (e.g., by means of UV-irradiators, a laser, etc.) in a manner known per se, depending on the type and presence, respectively of an initiator.
  • the process may also require a polishing step to remove excess material.
  • FC-1 [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHOC(O)NH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3
  • FC-2 [C 4 F 9 SO 2 N(CH 3 )CH 2 ] 2 CHO(CH 2 ) 3 Si(OCH 2 CH 3 ) 3
  • Test solutions for Examples 1 - 7 and Comparative Example C-1 were prepared by combining 1.0 g of the compositions listed in Table 1 together with 37% HCl (1.0 g) and ethanol (98.0 g).
  • Test Solutions were sprayed onto pre-cleaned, white sanitary ceramic tiles (available from Sphinx, Maastricht, Netherlands) at room temperature at a rate of about 40 mL/minute.
  • FC-1 (g) FC-2 (g) TEOS (g) MTEOS (g) DDS (g) FC-3* (g) 1 1.0 --- --- --- --- --- --- --- --- --- --- -- 3 0.5 --- 0.5 --- --- --- 4 0.10 --- 0.9 --- --- --- 5 0.10 --- 0.45 0.45 --- --- 6 0.10 --- 0.45 --- 0.45 --- 7 --- 0.10 0.90 --- --- C-1 --- --- --- --- --- --- 1.0 --- indicates none added FC-3 is C 8 F 17 SO 2 N(CH 2 CH 3 )CH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 3 Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Detergent Compositions (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass (AREA)
EP05854110A 2004-12-30 2005-12-15 Compositions containing c4-swallow tail silanes Not-in-force EP1831234B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/027,404 US7495118B2 (en) 2004-12-30 2004-12-30 Compositions containing C4-swallow tail silanes
PCT/US2005/045326 WO2006073718A1 (en) 2004-12-30 2005-12-15 Compositions containing c4-swallow tail silanes

Publications (2)

Publication Number Publication Date
EP1831234A1 EP1831234A1 (en) 2007-09-12
EP1831234B1 true EP1831234B1 (en) 2011-09-14

Family

ID=36168510

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05854110A Not-in-force EP1831234B1 (en) 2004-12-30 2005-12-15 Compositions containing c4-swallow tail silanes

Country Status (8)

Country Link
US (1) US7495118B2 (ja)
EP (1) EP1831234B1 (ja)
JP (1) JP4988598B2 (ja)
CN (1) CN101094859B (ja)
AT (1) ATE524480T1 (ja)
CA (1) CA2592284A1 (ja)
RU (1) RU2007123147A (ja)
WO (1) WO2006073718A1 (ja)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7629298B2 (en) * 2006-02-21 2009-12-08 3M Innovative Properties Company Sandstone having a modified wettability and a method for modifying the surface energy of sandstone
US7569715B2 (en) * 2006-07-05 2009-08-04 3M Innovative Properties Company Compositions containing silanes
DE602007005017D1 (de) * 2006-10-20 2010-04-08 3M Innovative Properties Co Verfahren für leicht zu reinigende substrate und artikel daraus
BRPI0719929A2 (pt) 2006-12-07 2014-03-11 3M Innovative Properties Co Partículas que compreendem um siloxano fluorado e métodos de preparo e uso das mesmas
US8058463B2 (en) 2007-12-04 2011-11-15 E. I. Du Pont De Nemours And Compnay Fluorosilanes
WO2009086515A2 (en) 2007-12-27 2009-07-09 3M Innovative Properties Company Protective coating compositions
US20110020657A1 (en) * 2007-12-27 2011-01-27 Cheng-Chung Chang Protective coating compositions
TWI450043B (zh) * 2008-03-11 2014-08-21 3M Innovative Properties Co 具備保護層之光工具
US9096712B2 (en) 2009-07-21 2015-08-04 3M Innovative Properties Company Curable compositions, method of coating a phototool, and coated phototool
KR101768237B1 (ko) 2009-09-16 2017-08-14 쓰리엠 이노베이티브 프로퍼티즈 컴파니 플루오르화된 코팅 및 그로 제조된 포토툴
KR101781659B1 (ko) 2009-09-16 2017-09-25 쓰리엠 이노베이티브 프로퍼티즈 컴파니 플루오르화된 코팅 및 그로 제조된 포토툴
US8420281B2 (en) 2009-09-16 2013-04-16 3M Innovative Properties Company Epoxy-functionalized perfluoropolyether polyurethanes
CN107001397B (zh) 2014-09-26 2020-10-13 科慕埃弗西有限公司 异氰酸酯衍生的有机硅烷

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2153270A1 (de) * 1971-10-26 1973-05-03 Bayer Ag Perfluoralkansulfonamide

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803615A (en) * 1956-01-23 1957-08-20 Minnesota Mining & Mfg Fluorocarbon acrylate and methacrylate esters and polymers
US3442664A (en) * 1966-04-26 1969-05-06 Minnesota Mining & Mfg Treating composition,method of treating and treated surfaces
US3492394A (en) * 1966-10-03 1970-01-27 Minnesota Mining & Mfg Molding capable of providing multiple release of articles therefrom and of using same
US3423234A (en) * 1967-04-14 1969-01-21 Minnesota Mining & Mfg Dripless container coated with fluoroaliphatic siloxanes
US3787351A (en) * 1972-02-28 1974-01-22 Minnesota Mining & Mfg Use of soluble fluoroaliphatic oligomers in resin composite articles
DE2238740C3 (de) * 1972-08-05 1981-07-16 Bayer Ag, 5090 Leverkusen Perfluoralkylgruppenhaltige Polyäther und Verfahren zu deren Herstellung und deren Verwendung
US3919295A (en) * 1973-04-16 1975-11-11 Bayer Ag Preparation of inorganic fluoride-free perfluoroalkane sulphonates
US4167639A (en) * 1973-06-09 1979-09-11 Hoechst Aktiengesellschaft Fluorinated sulfosuccinates
US4226738A (en) * 1978-11-01 1980-10-07 American Cyanamid Company N,N-Bis(trifluoromethylsulfonyl)oxamides and chemiluminescent compositions containing the same
JPS60126203A (ja) 1983-12-12 1985-07-05 Shin Etsu Chem Co Ltd ナメクジ・マイマイ防除剤およびこれを使用する農作物・果樹保護方法
JPS61275180A (ja) * 1985-05-31 1986-12-05 株式会社　信光社 サフアイヤナイフの表面改質法
GB2218097A (en) 1988-04-26 1989-11-08 Mitsubishi Metal Corp Perfluoroalkylsulphonamidoalkyl silanes; surface treatment agents
JP2605340B2 (ja) * 1988-04-26 1997-04-30 三菱マテリアル株式会社 含フッ素シラン化合物およびその製造方法
US5207996A (en) * 1991-10-10 1993-05-04 Minnesota Mining And Manufacturing Company Acid leaching of copper ore heap with fluoroaliphatic surfactant
DE4217366A1 (de) * 1992-05-26 1993-12-02 Bayer Ag Imide und deren Salze sowie deren Verwendung
DE4241478A1 (de) * 1992-12-09 1994-06-16 Bayer Ag Fluorierter Carbonsäureester von Phosphono- und Phosphinocarbonsäuren sowie deren Verwendung
US5274159A (en) * 1993-02-18 1993-12-28 Minnesota Mining And Manufacturing Company Destructable fluorinated alkoxysilane surfactants and repellent coatings derived therefrom
US5874616A (en) * 1995-03-06 1999-02-23 Minnesota Mining And Manufacturing Company Preparation of bis (fluoroalkylenesulfonyl) imides and (fluoroalkysulfony) (fluorosulfonyl) imides
US5688884A (en) * 1995-08-31 1997-11-18 E. I. Du Pont De Nemours And Company Polymerization process
US5702509A (en) * 1995-12-22 1997-12-30 Minnesota Mining And Manufacturing Company Masonry treatment composition
US6156860A (en) * 1997-02-18 2000-12-05 Dainippon Ink And Chemicals, Inc. Surface active agent containing fluorine and coating compositions using the same
US6514493B1 (en) * 1997-07-21 2003-02-04 University Of Pittsburgh Of The Commonwealth System Of Higher Education cDNA clone for tumor rejection antigen gp110 and tumor peptide vaccine
EP1044478A1 (en) * 1997-12-10 2000-10-18 Minnesota Mining And Manufacturing Company Bis(perfluoroalkylsulfonyl)imide surfactant salts in electrochemical systems
US6514492B1 (en) 1999-07-14 2003-02-04 Schering-Plough Veterinary Corporation Taste masking of oral quinolone liquid preparations using ion exchange resins
WO2001030873A1 (en) 1999-10-27 2001-05-03 3M Innovative Properties Company Fluorochemical sulfonamide surfactants
US6452038B1 (en) * 2000-06-28 2002-09-17 3M Innovative Properties Company Fluoroalkyloxy dispersant
AU2001283381A1 (en) 2000-08-18 2002-03-04 3M Innovative Properties Company Fluoroalkyl (meth)acrylate copolymer coating compositions
ES2282186T3 (es) 2001-01-19 2007-10-16 3M Innovative Properties Company Silanos fluoroquimicos solubles en agua o dispersables en agua para hacer que un sustrato sea repelente al aceite y al agua.
ATE432298T1 (de) 2001-01-19 2009-06-15 3M Innovative Properties Co Fluorovinyloligomerkomponente mit silangruppen, flüssigzusammensetzungen daraus und beschichtungsverfahren
US6689854B2 (en) * 2001-08-23 2004-02-10 3M Innovative Properties Company Water and oil repellent masonry treatments
US6861149B2 (en) * 2001-11-27 2005-03-01 3M Innovative Properties Company Compositions for aqueous delivery of self-emulsifying fluorinated alkoxysilanes
US6890360B2 (en) * 2001-12-17 2005-05-10 3M Innovative Properties Company Fluorochemical urethane composition for treatment of fibrous substrates
EP1329548A1 (en) 2002-01-21 2003-07-23 3M Innovative Properties Company Method of treatment of a textile or non-woven substrate to render same water and oil repellent
US7078454B2 (en) 2002-04-17 2006-07-18 3M Innovative Properties Company Repellent fluorochemical compositions
ATE346884T1 (de) 2002-06-03 2006-12-15 3M Innovative Properties Co Fluor-silan-oligomerzusammensetzung
US6903173B2 (en) 2002-08-02 2005-06-07 3M Innovative Properties Co. Fluorinated polymers
US7727710B2 (en) * 2003-12-24 2010-06-01 3M Innovative Properties Company Materials, methods, and kits for reducing nonspecific binding of molecules to a surface
WO2005066224A1 (en) * 2003-12-31 2005-07-21 3M Innovative Properties Company Water-and oil-repellent fluoroacrylates
US7160850B2 (en) * 2004-12-30 2007-01-09 3M Innovative Properties Company Compositions of monomeric surfactants
US7776983B2 (en) * 2004-12-30 2010-08-17 3M Innovative Properties Company Fluorochemical polymeric surfactants
US20070197401A1 (en) * 2006-02-21 2007-08-23 Arco Manuel J Sandstone having a modified wettability and a method for modifying the surface energy of sandstone
US7569715B2 (en) * 2006-07-05 2009-08-04 3M Innovative Properties Company Compositions containing silanes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2153270A1 (de) * 1971-10-26 1973-05-03 Bayer Ag Perfluoralkansulfonamide

Also Published As

Publication number Publication date
CA2592284A1 (en) 2006-07-13
JP2008527079A (ja) 2008-07-24
RU2007123147A (ru) 2009-02-10
US7495118B2 (en) 2009-02-24
JP4988598B2 (ja) 2012-08-01
CN101094859A (zh) 2007-12-26
CN101094859B (zh) 2010-09-29
EP1831234A1 (en) 2007-09-12
ATE524480T1 (de) 2011-09-15
US20060147645A1 (en) 2006-07-06
WO2006073718A1 (en) 2006-07-13

Similar Documents

Publication Publication Date Title
EP1831234B1 (en) Compositions containing c4-swallow tail silanes
US6613860B1 (en) Compositions comprising fluorinated polyether silanes for rendering substrates oil and water repellent
EP1444289B1 (en) Coating composition comprising fluorochemical polyether silane polycondensate and use thereof
KR102089108B1 (ko) 퍼플루오로폴리에테르 변성 폴리실라잔 및 그의 제조 방법, 표면 처리제, 및 상기 표면 처리제로 처리된 물품
EP1444305B1 (en) Coating composition comprising a fluorochemical polyether silane partial condensate and use thereof
EP1813640B1 (en) Fluorine-containing organopolysiloxane, a surface treatment composition comprising the same and an article treated with the composition
ES2277985T3 (es) Composicion de oligomero de fluoro-silano.
JP5007812B2 (ja) パーフルオロポリエーテル変性アミノシランを含む表面処理剤並びに該アミノシランの硬化被膜を有する物品
TWI558678B (zh) 抗油性塗層
EP2780426B1 (en) Fluorinated coatings with lubricious additive
KR20190003632A (ko) 조성물
US7569715B2 (en) Compositions containing silanes
JP3774917B2 (ja) 含フッ素有機ケイ素化合物
JPS58129082A (ja) ガラス表面の撥水撥油剤
JP6215389B2 (ja) 撥水撥油性組成物、及びそれを用いて形成した撥水膜
CN117500863A (zh) 含氟醚化合物、含氟醚混合物、涂布剂、物品及物品的制造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070627

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20080919

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602005030079

Country of ref document: DE

Effective date: 20111110

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111215

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 524480

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120114

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120116

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20120615

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20111215

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602005030079

Country of ref document: DE

Effective date: 20120615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111215

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111231

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20131211

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20131209

Year of fee payment: 9

Ref country code: IT

Payment date: 20131213

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005030079

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141215